Suspensions of chlorinated materials and methods of making the same



Patented Feb. 7, 1950 suspensions or crmonmnran Marsamps AND neurons or MAKING rm:

Painesvllle, Ohio, assignor to Company, Cleveland, Ohio, I

Harr S. 01ml,

Diamond 'Alkali corporation of Delaware No Drawing. Application October a, rm,

, Serial No. 702,088

5Claims. (c1. zoo-28.5) T

. 1 This invention relates to highly chlorinated d in particular relates to of such highly chlorinated making the same. type of material to which organic materials an suspensions in water ces and to methods of As an example of the the like whereby their application for various industrial purposes is enhanced. They have as a particular advantage the fact that the suspending process imports to the material no more color than was present in the originalunsuspended the present inventi on is particularly applicable may be cited chlo rinated paraflin containing 65% e. Organic materials having age of chlorine are normally elevated temperatures and thus ently be emulsified with water. re been proposed to form a soluorinated materials in an organic ample, toluol, and then to combine with water unde solids at relatively may not conveni such solution ing themselves to Without regard the use of an org on which render many industri ammable and th solvents is undesirable o standpoint, because of lack proper safeguards to handle t Such industries have heretof vantages of using such big terials, such as chlorinated lied or suspended r conditions lendthe formation of an emulsion. to the success of s c solvent is a limitation theres the procedure unacceptable to es, particularly industries where the us dangerous organic from the practical of equipment and he same, impossible. e foregone the adhly chlorinated maparafiin, in an emulsiform because of this disaduch practices,

ntemplates the soluthe provision of a d materials in water olvents. More parntemplates the protion of matter comchlorinated to more in which form they approaching the boilpermanently and stably The present invention co tion of this difliculty and suspension of such chlorinate without the use of organic s ticularly, the invention co vision of a novel composi prising organic materials than 65% of their weight are solids at temperatures ing point of water, suspendedinwater. It

chlorinated material. v

The suspensions of this invention have particular application in many industries where the use of organic solvents became of fire hazards, toxicity, and the like is undesired.- For example, they have wide application in the paper industry where it is often desired to incorporate highly chlorinated paraflin into paper to impart water resistance or flame resistance or other properties to the paper. Chlorinated has a similar application in the rubber industry in both natural and synthetic latex emulsions to impart increased adhesion and flame resistance to adhesive materials and here the provision of a suspension 1 of chlorinated material without use of organic solvents is highly desirable. The suspensions of this invention are also applicable in the impregnation of wood and in the fabrication or various waxes, polishes, and other surface improving materials. They may also be applied to waterproofing compositions, aswell as to asphalt emulsions for paints and similar surface preserving compositions. From the recitation of these various specific proposed applicatio'm, it will be apparent to those skilled in the art that by the provision of an organic-solvent-free suspension of highly chlorinated organic materials in water. there has been produced a material which will broaden the field of application or the chlorinated materials themselves.

It has been found that in order to produce optimum results, a suspending agent is desirably I incorporated with the chlorinated hydrocarbon material during the time the material is being "treated in order to reduce its particle size, and for has been found in general invention may be achieved orinated materials, such into particles having an 10 microns or less in the suspending agent and subdivided in the presstable, non-breaking suspensions may be tantially to infinity with eaking. The suspensions, furbie to dilute acids and aikalies severe temperature changes of the freezing and boiling The suspensions are further und to be compatible with oils, plasticizers,

that the objects of this by subdividing solid 0 as chlorinated paraflin, average diameter size of presence of a suitable water and that when so ence of such agent, pensions are obtains suitably diluted subs water without br thermore, are sta and to relatively within the range points of water.

d, which sus this purpose it is preferred to use polyvinyl alcohol. Polyvinyl alcohol is a material of varying molecular weight depending upon the degree of polymerization presentin a particular sample and it may conveniently be made by the saponification of polyvinyl acetate according to a process which does not form a part of the present invention. The character and properties of polyvinyl alcohols'are generally identified by reference to comparative viscosities of the polymerized materials and while it has been found that all polyvinyl alcohols are suitable for ap plication to the present invention, those substantially completely saponifled materials having a and 65 viscosity averaging approximately 50 centipoises mul s 3 1 ina4% solutioninwateratflil 0.,hayc given optimumresults.

mmefliodofreducinstlieparticlesizeofthe chlorinated materials herein disclosed, which has been found most useful, is relatively extended ball milling employing flint, or darkening of color is not but various types of mixers, homogenizers, colloid and the like particularly those having a shearing or cutting action in addition to their mixing function, have also been found useful and their use has resulted in excellent stable suspensions in much shorter times than can be obtained by ball milling. The invention, however, is not limited to the specific type of particle size reducer involved as many other convenient mills. mixers, grinders, and the like will suggest themselves to those skilled in the art.

In order more particularly to point out and disclose means in which this invention may be practiced, the following specific examples are set forth:

1. To 68% parts of water is added 1% parts of polyvinyl alcohol of the completely saponifled typehavingaviscosityoffilcentipoisesinadet solution in water at 20 C. and while mixing, so parts of chlorinated paraffin containing between 69 and 71% chlorine are added. The mixture is milled for 66 hours ina ball mill employing flint balls, and upon removal from the mill is found to comprise a suspension stable over long periods of time without breaking. After several days of standing, a slight settling is observed which is readily resuspended by shaking by hand. The suspension is diluted with 100 parts of water and found not to break. v

2. A mixture of 50 parts of chlorinated parafiln containing 69-71% chlorine, 1% parts of polyvinyl alcOhOl as in Example 1, and 48% parts of water is milled in a ball mill employing steel balls for a. period of 42 hours. On removal from the mill, the material is found to comprise asemisolid mass dilutable in all proportions with water without breaking the suspension. The suspension is further found to be substantially stable for long periods of time whether in its original form or diluted with water.

As noted above, suspensions in water of chlorinated materials, particularly chlorinated paraffins, where the chlorine content is of the order of 65 to 85% are highly useful, particularly in the paper industry, for forming flameprooflng mixtures to be applied to paper and the following example sets forth a method for compounding such flameprooflng mixture.

3. A mixture of 20 parts of solid chlorinated paraffin, 20 parts of calcium carbonate, parts of antimony oxide, 2 parts of polyvinyl alcohol as in Example 1, and 48 parts of water is ball.

milled at room temperature for a period of 24 hours employing flint balls. The product on being removed from the mill is a thick fluid suspension showing excellent stability over long periods of time and dilutable in all proportions with water. This material when applied to paper renders it substantially flame-resistant.

For some purposes to which the suspensions of this invention are applied, it has been found useful to employ a stabilizer for the suspension which, when the particles of chlorinated materials are sufiiciently finely divided and suspended by any of the methods set forth above, will stabilize the suspension against even the small amount of settling noted, for example, above in connection with Example 1.

inthecasewhere slight important; steel bails,

stabilizers are cetyl alcohol, methyl cellulose, gum tragacanth, gum arable, and Karaya gum. Amounts of such stabilizers up to 2% of the total canth as a stabilizer, which material is preferred in this connection, is as follows:

4. A mixture of 30 parts of solid chlorinated paraflin, 1 parts of polyvinyl alcohol, /2 part of gum tragacanth, and 68 parts of water is ball milled at room temperature for a period of 42 hours. At the end of this time a stable, thick suspension is obtained which is dilutable in all proportions with water without breaking and may be stored indefinitely without substantial settling.

As suggested above, the importance of the milling or mixing treatment does not lie in the'type of equipment employed nor in the length of time the suspensions are treated but rather in the reduction of the particles of chlorinated materials to the proper size which will enable them to remain suspended for suitable periods of time. An example of treatment of chlorinated materials in a different type of equipment wherein substantially the same action is obtained follows:

5. 30 parts of 69 to 71% chlorinated par-aflln are combined with 1%; parts of polyvinyl alcohol of the type described in Example 1, and /2 part of Karaya gum. This mixture is added to 68 parts of water at room temperature and the whole is stirred in a high speed mixing device (the "Homo-Mixer, manufactured by Eppenhach,

Inc., of Long Island City, New York) having provision for exceedingly high impact of stirrer blades against the material treated. The mixing is continued for a period of '5 minutes. The material, when removed from the mixer, is a roletively viscous thickened fluid, the particles of which are of the average order of 10 microns in diameter. The suspension is found to be stable on standing for periods up to 10 days, during which time no breaking and very little settling occurs.

The preferred chlorinated materials to which this invention is directed are chlorinated hydrocarbons, particularly chlorinated paramn containing more than of chlorine. Chlorinated parafiins containing from 60 to 11% of chlorine have been found to be particularly useful. In addition, stable organic-solvent-free dispersions may be formed by the method of this invention of various other chlorinated materials which have been chlorinated to the extent that their melting points are equal to or exceed the boiling point of water whereby emulsions with water cannot be formed directly. Examples of such materials are chlorinated polyethylene, polyvinyl chlorides, chlorinated corn oil, sunflower oil, coconut oil, olive oil, peanut oil, mustard seed oil, perllla oil, linseed oil, and rapeseed oil. The dispersions of these materials so formed can be diluted with large volumes of water without breaking the suspension.

While there have been described various embodiments of the invention, the methods and products described are not intended to be understood as limiting the scope of the invention as it is realized that change therewithin are possible and it is further intended that each element recited in any of the following claims is to be understood as referring to all equivalent elements for accomplishing substantially the same results in substantially the same or equivalent manner, it being intended to cover the invention broadly Examples of such It in whatever form its principle may be utilized.

milling to suspend said chlorinated paraflin in the water.

2 The method of forming a stable aqueous dispersion of chlorinated paraflin having a chlorine content of more than 65%, which includes the steps of combining said chlorinated paraflln with polyvinyl alcohol and milling said mixture in the presence of water until the particle size of said 3. A composition of matter comprising a stable aqueous suspension of solid, chlorinated, paramn having a chlorine content of more than 65% and polyvinyl alcohol, said chlorinated material having a particle size of the average order of not more than 10 microns.

REFERENCES CITED The following references are of record in the file of this patent:

V UNITED STATES RA Number Name Date 2,277,788 Shipp et al Mar. 31, 1942 2,413,163 Bacon Dec. 24, 1946 OTHER REFERENCES Polyvinyl Alcohol, Procedure for Emulsifying Opalwax," E. I. du Pont de Nemours and Company, R. and M. Chemicals Div., Wilmington, Del, January 10, 1941, page 1. 

1. THE METHOD OF FORMING A STABLE AQUEOUS DISPERSION OF SOLID, HIGHLY CHLORINATED, PARAFFIN CONTAINING AT LEAST 65% OF CHEMICALLY COMBINED CHLORINE, WHICH INCLUDES THE STEPS OF COMBINING SAID MATERIAL WITH A DISPERSING AGENT COMPRISING POLYVINYL ALCOHOL AND SUBJECTING SAID MIXTURE TO MILLING TO SUSPEND SAID CHLORINATED PARAFFIN IN THE WATER. 